Vulcanization accelerators



1 Patented Oct. 9, 1945 UNITED "STATE PATENT OFFICE 'VULCANIZATION ACCELERATORS Roy ShHanslick. Wyndmoor, Pa., assignor to United States Rubber Company, New York, I N. 3L, a corporation of New Jersey No Drawing. Application January 14, 1943,-

. Serial No. 472,401

. q q 3 Claims. (01. 260-247) V This invention relates to anew class of compounds which have been found valuableas accelerators of the vulcanization of rubber and particularly as activators of accelerators of the mercaptobenzothiazole class.

This case is a continuation of my application Serial No. 280,445, filed June 22, 1939, now Patent No. 2,285,813, dated June 9, 1942, and of my copending application Serial No. 334,174.1-1led May 9,1940, Patent.2,318,482.

The new class of rubber vulcanization accelera- .mole) of sodium di-n-butyl dithiocarbamate is groups are the alkyl groups including those having an aryl group attached to the far side of the alkyl group such as benzyl. The reaction is carried outat temperatures between 0 and 100 C. and preferably between 0 and 10 C. The resulting products are called thiocarbamyl sulfamines comprising the group The following examples are given to illustrate the invention: EXAMPLE I A water solution containing 42.9 grams (0.3 mole) of sodiumdimethyl dithiocarbamate is cooled to 05 C. by means of an ice-water bath. A freshly prepared water solution containing 15.5 grams (0.3 mole) plus 10% excess of monochloramine chilled to 0-5" 0., is slowly added to the aqueous sodium 'dimethyl dithiocarbamate solution. Rapid stirring is employed. Upon the complete addition of the aqueous monochloramine solution, stirring is continued for five to ten minutes whereupon the white material is then filtered ofi and washed with water. The material is then dried. Melting point is 70-71 C. (uncorrected). Dimethyl thiocarbamyl sulfamine is obtained in a yield of 39-405 grams.

The reaction maybe expressed as follows:

CH3 s H 7 r H N-C-S-Na M1201 N-O-S-NH; NaOl CH3 CH3 Analysis Theory Obtained Percent Percent Nitrogen 20. 4 20. 2 Qnlfm' I 45. 6 46. 1

1 EXAMPLE II M A water solution containing 22.7 grams (0.1

cooled to 05 C. 5.15 grams (0.1 mole) plus 10% excess of monochloramine in aqueous solutionis added. with goodstirring of the mixturesolution.

.A white precipitate is formed which is filtered off, washed with water and then dried. The material is low melting. Di-n-butyl thiocarbamyl sulfamine is obtained in a yield of 20-215 grams.

EXAMPLE III A water solution containing 31.1 grams (0.1 mole) of potassium dibenzyl dithiocarbamate is cooled to 0-5 C. A freshly prepared solution of 5.15 grams (0.1 mole) plus 10% excess-of monochloramine in aqueous solution is added to the potassium dithiocarbamate solution. A precipitate separates and the solution is well stirred.

7 The material is filtered off, Washed with Water and then dried. Melting point is 66-69? C. (uncorrected). Dibenzyl thiocarbamyl sulfamine is obtained in a yield of 27-285 grams.

' Analysis Theory Obtained Percent Percent Nitrogen 9. 8. 9 Sulfur 22. 2 20. 2

Similarly compounds such as oxy-di-ethylene thiocarbamyl sulfamine (melting point l26-128 C. (uncorrected)) and cyclo 'penta methylene thiocarbamyl sulfamine (melting point 43-44 C. (uncorrected)) may be prepared.

Instead of sodium or potassium salts of dithiocarbamic acids, there may be used the ammonium, calcium, barium, and other metal salts for reaction with chloramine.

The dithiocarbamate employed to react with monochloramine may be N-substituted with various groupings such as ethyl, propyl,isopropy1, isobutyl, amyl, isoamyl, phenyl, cyclohexyl, phenyl ethyl, heterocyclic radicals from morpholine, and piperidyl, such as cyclopentamethylene and oxydi-ethylene.

In the preferred compounds, namely the dialkyl substituted dithiocarbamates, which are used to react with monochloramine, the alkyl groups may be any of the above referred to alkyl groups, and the alkyl groups may be similar or dissimilar in any given compound, to produce the corresponding dialkyl thiocarbamyl sulfamines.

The following data illustrates the accelerating effect of the compounds; the parts are by weight:

T.=ultimate tensiles in pounds per square inch.

E=per cent elongation at break.

If desired, the new accelerators may be used with any of the well-known basic nitrogen-containing accelerators used in activating the accelerators of the mercapto thiazole type, including the guanidine and substituted guanidine salts, such as diphenyl guanidine salt of aliphatic and aromatic acids.

The present accelerators are best used in conjunction with arylene thiazyl sulphide accelerators such as mercaptobenzothiazole and its derivatives, including its salts, such as those of zinc. In this connection the two accelerators may be added separately on the mill or they may be mixed prior to addition on the mill. 7

The term rubber herein is to be understood as including caoutchouc, and similar vulcanizable gums, natural or synthetic, including latices thereof.

The present invention is not limited to the specific examples above set forth wherein the preferred accelerator is employed. Other ratios of the compounding ingredients than those mentioned in the examples as well as other well known fillers, pigments and the like may be employed in the production of various types of rubber compounds as Will be apparent to those skilled in the art to which this invention pertains.

Having. thusdescribed my invention, what I claim: and desire to protect by Letters Patent is:

.1. As a new compound, a thiocarbamyl sulfamine having the formula CH2'OH2/ where Y is a member of the group consistin of oxygen and --CH2. 7

2. As a new compound, a thiocarbamyl sulfamine having the formula 3. As a new compound, a thiocarbamyl sulfamine having the formula ROY S. HANSLICK. 

